JP4964056B2 - Curable composition - Google Patents

Description

  The present invention relates to a curable composition useful as a waterproofing material, an adhesive, and a sealing material in architecture, civil engineering, industrial use, and the like.

  Asphalt is excellent in tackiness, workability and waterproofness, and is an inexpensive and easy-to-use material, so it can be used in fields such as road paving materials, roofing materials, sealing materials, adhesives, waterway lining materials, vibration damping materials, and soundproofing materials. Widely used.

  For example, when asphalt is used as a roofing material, a number of so-called asphalt waterproof thermal methods for forming a waterproof layer by laminating a plurality of asphalt sheets with hot asphalt have been used. Although the waterproofing reliability of the construction method is very high, there is an environmental problem that a lot of smoke and odor is generated when melting asphalt and the surrounding environment is significantly polluted. The number of properties that are shunned and adopted is decreasing. In addition, there is a danger that the operator may burn, and there is a tendency to avoid the safety of the operator.

  In order to overcome such problems of the thermal method, the use of an asphalt waterproof sheet having an adhesive layer as a cooling method is spreading. However, there are problems such as the waste material of the release paper generated at the time of construction and the adhesive layer being incompletely adhesive with the base and causing water leakage.

  As a cooling method, other asphalts are diluted with a solvent and the asphalt sheet is bonded by using solvent-based asphalt adjusted to a viscosity that can be applied at room temperature or water-based asphalt in which asphalt is emulsified. However, solvent-based asphalt has various problems such as environmental problems associated with odor and volatilization due to the solvent, and further, sufficient adhesiveness does not appear until the solvent volatilizes. In addition, the water-based asphalt composition has problems such as a decrease in curability in winter and a problem that the final adhesive strength cannot be sufficiently secured.

In order to improve such problems, solvent-free and non-aqueous curable compositions by mixing asphalt and organic polymers having reactive silicon groups have been proposed (Patent Documents 1 to 4). However, although the disadvantages of the solvent-based asphalt composition and the water-based asphalt composition have been improved by the composition, the stability of the system is lowered in the low viscosity composition with improved workability, and separation phenomenon is observed after storage. For example, there is a problem that sufficient storage stability cannot be obtained. The separation after storage in this case refers to a phenomenon in which a liquid component composed of a low-viscosity component is separated during storage of the composition in a closed container.
US2005-0107499 gazette WO2006-046472 WO2006-046473 WO2006-046474

  The problem to be solved by the present invention is a defect of the solvent-based asphalt composition and the water-based asphalt composition, and it has good workability and storage stability while ensuring physical properties such as solvent-free, fast curing, adhesiveness, etc. Is to provide a curable composition.

  As a result of intensive studies by the present inventors in order to solve the above problems, it has been found that the following curable composition is effective.

That is, the present invention
(A) The following general formula (1):
—Si (R ¹ _3-a ) X _a (1)
(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, X represents a hydroxyl group or a hydrolyzable group. 2 or 3 is shown.)
100 parts by weight of an organic polymer having a reactive silicon group represented by
(B) In one molecule, the following general formula (2):
—Si (R ² _3-b ) X ² _b (2)
(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and X ² represents a hydroxyl group or a hydrolyzable group. 2 or 3)) 0.1-20 parts by weight of a silane coupling agent having a reactive silicon group and an amino group represented by
(C) 1 to 200 parts by weight of asphalt,
(D) 10 to 120 parts by weight of a plasticizer,
(E) 1-30 parts by weight of hydrophobic finely divided silica,
(F) Viscosity (2 rpm, rotor No. 7, BS type viscometer) containing 10 to 500 parts by weight of inorganic filler (G) 0.1 to 10 parts by weight of curing catalyst and measured by a method according to JIS K 7117 ) Relates to a curable composition having a temperature of 23 Pa and 800 Pa · s or less.

  Preferably, it relates to a curable composition containing 1 to 80 parts by weight of (H) tackifying resin.

  More preferably, the curable composition wherein the component (A) is a polyoxyalkylene polymer (a1) and / or a vinyl polymer (a2) having a reactive silicon group represented by the general formula (1). About.

  More preferably, it relates to a curable composition in which the main chain skeleton of the component (a1) is a polyoxypropylene polymer.

  More preferably, it relates to a curable composition in which the main chain skeleton of the component (a2) is a (meth) acrylic acid alkyl ester copolymer.

  More preferably, the present invention relates to a curable composition in which the weight percent of asphaltenes contained in the asphalt that is component (C) is 10% by weight or less.

  More preferably, it relates to a curable composition in which the component (E) is a surface-treated fumed silica.

  More preferably, the component (H) is at least one of a terpene phenol resin, an aromatic hydrocarbon resin, a mixed aliphatic / aromatic hydrocarbon resin, or a resin obtained by modifying these with (alkyl) phenol. It relates to a curable composition.

  More preferably, it relates to a curable composition in which the component (G) is an ester compound.

  More preferably, the viscosity (2 rpm, rotor No. 7, BS type viscometer) measured by a method according to JIS K 7117 is 500 Pa · s or less at 23 ° C. Relates to the composition.

  Moreover, it is related with the waterproof material which uses the curable composition in any one of the said.

  Moreover, it is related with the adhesive agent which uses any one of the said curable compositions.

  Moreover, it is related with the sealing material which uses the curable composition in any one of the said.

  According to the present invention, it is possible to obtain a curable composition that does not generate smoke or odor and is excellent in workability, curability, adhesiveness, and storage stability.

  The curable composition of the present invention comprises (B) a silane coupling agent having a reactive silicon group and an amino group in an amount of 0.1 to 20 with respect to 100 parts by weight of the organic polymer having (A) a reactive silicon group. Parts by weight, (C) 1 to 200 parts by weight of asphalt, (D) 10 to 120 parts by weight of plasticizer, (E) 1 to 20 parts by weight of hydrophobic fine silica, and (F) 10 to 500 parts by weight of inorganic filler. Part (G) 0.1-10 parts by weight of a curing catalyst, and a viscosity (2 rpm, rotor No. 7, BS type viscometer) measured by a method according to JIS K 7117 is 800 Pa at 23 ° C. -It is characterized by being less than s.

  In the curable composition of this invention, it is possible to express the characteristic characteristic of the polymer by the kind of organic polymer (A) which has a reactive silicon group.

  The organic polymer (A) having a reactive silicon group is not particularly limited. For example, the main chain skeleton thereof is an organic material such as a generally known polyoxyalkylene polymer, vinyl polymer, or polyester polymer. Polymers can be used. In particular, the polyoxyalkylene polymer (a1) having a reactive silicon group and / or the vinyl polymer (a2) having a reactive silicon group are suitable for the workability and curability of the composition, the mechanical properties of the cured product, It is preferable in terms of adhesiveness and the like.

The reactive silicon group of the polyoxyalkylene polymer (a1) having a reactive silicon group used as the component (A) of the present invention is not particularly limited, and representative examples thereof are as follows: For example, the general formula (1):
—Si (R ¹ _3-a ) X _a (1)
(R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, or an aralkyl group having 7 to 10 carbon atoms, X represents a hydroxyl group or a hydrolyzable group. A represents 1, 2 or 3 is represented).

  The hydrolyzable group represented by X is not particularly limited, and any conventionally known hydrolyzable group can be suitably used. Specific examples include a hydrogen atom, a halogen atom, an alkoxy group, an acyloxy group, a ketoximate group, an amino group, an amide group, an acid amide group, an aminooxy group, a mercapto group, and an alkenyloxy group. Alkoxy groups such as a methoxy group are particularly preferred from the viewpoint of mildness and easy handling.

  1 to 3 hydroxyl groups or hydrolyzable groups can be bonded to one silicon atom. When two or more hydroxyl groups are present in a reactive silicon group, they may be the same or different. good.

Specific examples of R ¹ in the general formula (1) include alkyl groups such as a methyl group and an ethyl group, cycloalkyl groups such as a cyclohexyl group, aryl groups such as a phenyl group, and aralkyl groups such as a benzyl group. . R ¹ is particularly preferably a methyl group.

  Although it does not restrict | limit especially as a reactive silicon group, A dimethylmonomethoxysilyl group, a methyldimethoxysilyl group, a trimethoxysilyl group, a methyldiethoxysilyl from the point with a high hydrolytic activity and a moderate hydrolyzability and easy to handle. It is preferably at least one selected from the group consisting of a group, an ethyldiethoxysilyl group, and a triethoxysilyl group.

As the main chain structure of the polyoxyalkylene polymer (a1) having a reactive silicon group of the present invention, the general formula (3):
—R ³ —O— (3)
(R ³ represents a divalent organic group having 1 to 20 carbon atoms containing one or more selected from the group consisting of hydrogen, oxygen, and nitrogen as constituent atoms.)
Any polymer may be used as long as the structure represented by the formula is a repeating unit. Moreover, the homopolymer in which all the repeating units are the same may be sufficient, and the copolymer containing a 2 or more types of repeating unit may be sufficient. Further, the main chain may have a branched structure.

  The main chain polymer of the polyoxyalkylene polymer (a1) having a reactive silicon group is a monoepoxy compound in the presence of various polymerization catalysts, starting from dihydric alcohol or polyhydric alcohol and various oligomers having a hydroxyl group. Is obtained by ring-opening polymerization.

  Specific examples of the initiator include, for example, ethylene glycol, propylene glycol, butanediol, hexamethylene glycol, methallyl alcohol, hydrogenated bisphenol A, neopentyl glycol, polybutadiene diol, diethylene glycol, triethylene glycol, polyoxyethylene glycol, poly Examples include oxypropylene glycol (polyoxypropylene diol), polyoxypropylene triol, polyoxypropylene tetraol, dipropylene glycol, glycerin, trimethylol methane, trimethylol propane, pentaerythritol, polyoxypropylene diol and polyoxypropylene triol. It is done. In particular, it is preferable to use polyoxypropylene glycol or polyoxypropylene triol from the viewpoint of ease of production, but other materials may be used.

  Specific examples of the monoepoxy compound include ethylene oxide, propylene oxide, α-butylene oxide, β-butylene oxide, hexene oxide, cyclohexene oxide, styrene oxide, α-methylstyrene oxide and other alkylene oxides, and methyl. Examples thereof include alkyl or allyl or aryl glycidyl ethers such as glycidyl ether, ethyl glycidyl ether, isopropyl glycidyl ether, butyl glycidyl ether, allyl glycidyl ether, and phenyl glycidyl ether. In particular, it is preferable to use propylene oxide because it is easy to ensure workability of the finally obtained component (a1), flexibility after curing, adhesion, and the like, but other components may be used. .

  Specific examples of the polymerization catalyst include alkali catalysts such as KOH and NaOH, acidic catalysts such as trifluoroborane-etherate, double metal cyanide complex catalysts such as aluminoporphyrin metal complexes and cobalt cyanide zinc-glyme complex catalysts. Already known ones such as are used. In particular, the use of a zinc hexacyanocobaltate glyme complex catalyst, which is a complex metal cyanide complex catalyst with few side reactions, is preferred, but other than that may be used.

  Specific examples of such polymerization are represented by, for example, a polymerization method using an alkali catalyst such as KOH, for example, a complex obtained by reacting an organoaluminum compound and porphyrin described in JP-A-61-215623. Polymerization method using transition metal compound-porphyrin complex catalyst, for example, Japanese Patent Publication No. 46-27250, Japanese Patent Publication No. 59-15336, US Pat. No. 3,278,457, US Pat. No. 3,278,458, US Pat. No. 3,278,459, US Pat. No. 3,427,256, US Pat. No. 3, U.S. Pat. No. 3,427,335, and a polymerization method using a double metal cyanide complex catalyst, for example, a polymerization method using phosphazene disclosed in JP-A-11-60723. Among them, the polymerization method using a double metal cyanide complex catalyst and the polymerization method using phosphazene are high in color because they are hardly colored, and a polyoxyalkylene polymer having a narrow molecular weight distribution can be obtained even with a high molecular weight. The polyoxyalkylene polymer having a low molecular weight but a low viscosity is preferable because it has a feature.

In addition, the main chain polymer of the polyoxyalkylene polymer (a1) containing a reactive silicon group is a hydroxyl group-terminated polyoxyalkylene polymer that is a basic compound such as KOH, NaOH, KOCH ₃ , NaOCH _3. Can be obtained by chain extension with a bifunctional or higher functional alkyl halide such as CH ₂ Cl ₂ or CH ₂ Br ₂ . Moreover, the method etc. which chain-extend a hydroxyl-terminated polyoxyalkylene polymer with a bifunctional or trifunctional isocyanate compound are also mentioned.

  The method for introducing the reactive silicon group into the polymer terminal of the polyoxyalkylene polymer is not particularly limited, and various methods can be used. In particular, a method in which a polyoxyalkylene polymer having an alkenyl group at the terminal and a reactive silicon group-containing hydrosilane compound is reacted in the presence of a group 8 transition metal catalyst is preferred.

  Examples of the hydrosilane compound include halogenated silanes such as trichlorosilane, methyldichlorosilane, dimethylchlorosilane, and phenyldichlorosilane; trimethoxysilane, triethoxysilane, methyldiethoxysilane, methyldimethoxysilane, and phenyldimethoxysilane. Alkoxysilanes; acyloxysilanes such as methyldiacetoxysilane and phenyldiacetoxysilane; ketoximatesilanes such as bis (dimethylketoxymate) methylsilane and bis (cyclohexylketoxymate) methylsilane However, it is not limited to these. Of these, halogenated silanes and alkoxysilanes are particularly preferable.

  In addition to this, addition of a reactive silicon group-containing isocyanate compound to a hydroxyl group-terminated polyoxyalkylene polymer, reaction of an isocyanate group-terminated polyoxyalkylene polymer with a reactive silicon group-containing amine compound, It can also be obtained by reacting an oxyalkylene polymer with a reactive silicon group-containing mercaptan compound.

As a method for producing a polyoxyalkylene polymer having an alkenyl group at the terminal, a conventionally known method may be used. For example, a hydroxyl group-terminated polyoxyalkylene polymer is reacted with a compound having an alkenyl group to form an ether bond, Examples of the method include bonding by an ester bond, a urethane bond, and a carbonate bond. For example, when an alkenyl group is introduced by an ether bond, the polyoxyalkylene polymer is terminated with a hydroxyl group terminal such as -ONa or -OK, and then the general formula (4):
^{_{CH 2 = CH-R 4 -Y}} (4)
Or general formula (5):
_{^{CH 2 = C (R 5)}} -R 4 -Y (5)
(Wherein, R ⁴ is a divalent alkylene group having 1 to 10 carbon atoms, R ⁵ is an alkyl group having 10 or less carbon atoms, and Y is a halogen atom). It is done.

Examples of the method for converting the terminal hydroxyl group into an oxymetal group include a method of reacting with an alkali metal such as Na and K; a metal hydride such as NaH; a metal alkoxide such as NaOCH ₃ ; and an alkali hydroxide such as NaOH and KOH. It is done.

Specific examples of the unsaturated group-containing compound represented by the general formula (4) or (5) include
_{CH 2 = CH-CH 2 -Cl} , CH 2 = CH-CH 2 -Br, CH 2 = CH-C 2 H 4 -Cl, CH 2 = CH-C 2 H 4 -Br, CH 2 = CH-C _{3 H 6 -Cl, CH 2 =} CH-C 3 H 6 -Br, CH 2 = C (CH 3) -CH 2 -Cl, CH 2 = C (CH 3) -CH 2 -Br, CH 2 = C _{(CH 2 CH 3) -CH 2} -Cl, CH 2 = C (CH 2 CH 3) -CH 2 -Br, CH 2 = C (CH 2 CH (CH 3) 2) -CH 2 -Cl, CH 2 _{= C (CH 2 CH (CH} 3) 2) -CH 2 -Br, etc., and especially from the viewpoint of _{reactivity, CH 2 = CH-CH 2} -Cl, CH 2 = C (CH 3) -CH _2- Cl is preferred.

As a method for introducing an unsaturated group, addition to _{CH 2} = _CH-CH 2 - group and _{CH 2 = C (CH 3)} -CH 2 - isocyanate compound having a group such as a carboxylic acid, the use of the epoxy compounds You can also.

As the group 8 transition metal catalyst, a metal complex catalyst selected from group 8 transition metal elements such as platinum, rhodium, cobalt, palladium and nickel is used. For _{example, H 2 PtCl 6 · 6H 2} O, platinum - vinylsiloxane complex, a platinum - olefin complexes, Pt _{metal, RhCl (PPh 3) 3,} RhCl 3, Rh / Al 2 O 3, RuCl 3, IrCl 3, FeCl 3 , PdCl ₂ .2H ₂ O, NiCl _{2 and} the like can be used. From the viewpoint of hydrosilylation reactivity, any of H ₂ PtCl ₆ .6H ₂ O, platinum-vinylsiloxane complex, platinum-olefin complex can be used. It is particularly preferable.

  Such manufacturing methods are disclosed in, for example, Japanese Patent No. 1396791, Japanese Patent No. 1727750, Japanese Patent No. 2135575, and Japanese Patent Laid-Open No. 3-72527.

  The polyoxyalkylene polymer (a1) having a reactive silicon group may be linear or branched, or a mixture thereof. In addition, other monomer units may be included, but the structural unit represented by the general formula (3) from the viewpoint of having a moderately low viscosity and a cured product having appropriate flexibility However, it is preferably present in the polyoxyalkylene polymer in an amount of 50% by weight or more, preferably 80% by weight or more.

  The molecular weight of the polyoxyalkylene polymer (a1) having a reactive silicon group is not particularly limited, but the number average molecular weight in terms of polystyrene in gel permeation chromatography (GPC) measurement is 500 to 100,000. It is preferable. Furthermore, it is preferable that it is 1,000-70,000 from the ease of handling etc. When the number average molecular weight is less than 500, the cured product becomes brittle, and when the number average molecular weight exceeds 100,000, the viscosity of the polymer becomes too high.

  Further, in the contained polyoxyalkylene polymer (a1) having a reactive silicon group, the ratio (Mw / Mn) of the weight average molecular weight to the number average molecular weight is preferably 2.5 or less, more preferably. Is 2.0 or less, more preferably 1.6 or less. The molecular weight distribution can be measured by various methods, but is usually measured by the GPC method. The composition using the polyoxyalkylene polymer having a reactive silicon group with Mw / Mn of 2.5 or less has a low viscosity and exhibits good workability.

  Next, the vinyl polymer (a2) having a reactive silicon group that can be used as the component (A) of the present invention will be described. The main chain of the vinyl polymer (a2) can be obtained by controlled radical polymerization or free radical polymerization.

  First, the case of controlled radical polymerization will be described.

  The inventors have so far made numerous inventions relating to vinyl polymers having various crosslinkable functional groups at the ends of the polymer, methods for producing the same, curable compositions, and uses (JP-A-11-080249). JP-A-11-080250, JP-A-11-005815, JP-A-11-116617, JP-A-11-116606, JP-A-11-080571, JP-A-11-080570, JP-A-11-130931, JP-A-11-1000043, Special (See Kaihei 11-116763, JP-A-9-272714, JP-A-9-272715, etc.). Although it does not specifically limit as a vinyl polymer (a2) of this invention, All the polymers disclosed by the invention illustrated above can be used suitably.

  It does not specifically limit as a vinyl-type monomer which comprises the principal chain of the vinyl-type polymer (a2) of this invention, Various things can be used. For example, (meth) acrylic acid, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) acrylic acid-n-propyl, (meth) acrylic acid isopropyl, (meth) acrylic acid-n- Butyl, isobutyl (meth) acrylate, (tert-butyl) (meth) acrylate, n-pentyl (meth) acrylate, n-hexyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acryl Acid-n-heptyl, (meth) acrylic acid-n-octyl, (meth) acrylic acid-2-ethylhexyl, (meth) acrylic acid nonyl, (meth) acrylic acid decyl, (meth) acrylic acid dodecyl, (meth) Phenyl acrylate, toluyl (meth) acrylate, benzyl (meth) acrylate, 2-methoxyethyl (meth) acrylate (Meth) acrylic acid-3-methoxybutyl, (meth) acrylic acid-2-hydroxyethyl, (meth) acrylic acid-2-hydroxypropyl, (meth) acrylic acid stearyl, (meth) acrylic acid glycidyl, (meth) 2-aminoethyl acrylate, γ- (methacryloyloxypropyl) trimethoxysilane, ethylene oxide adduct of (meth) acrylic acid, trifluoromethylmethyl (meth) acrylate, 2-trifluoromethylethyl (meth) acrylate , 2-perfluoroethylethyl (meth) acrylate, 2-perfluoroethyl-2-perfluorobutylethyl (meth) acrylate, 2-perfluoroethyl (meth) acrylate, perfluoromethyl (meth) acrylate , (Perfluoromethylmethyl) (meth) acrylate, (me T) 2-perfluoromethyl-2-perfluoroethylmethyl acrylate, 2-perfluorohexylethyl (meth) acrylate, 2-perfluorodecylethyl (meth) acrylate, 2-perfluoro (meth) acrylate (Meth) acrylic monomers such as hexadecylethyl; aromatic vinyl monomers such as styrene, vinyltoluene, α-methylstyrene, chlorostyrene, styrenesulfonic acid and their salts; perfluoroethylene, perfluoropropylene, vinylidene fluoride Fluorine-containing vinyl monomers such as vinyl trimethoxysilane, vinyl triethoxysilane and other silicon-containing vinyl monomers; maleic anhydride, maleic acid, monoalkyl and dialkyl esters of maleic acid; fumaric acid, monoalkyl of fumaric acid Beauty treatment And maleic monomers such as maleimide, methylmaleimide, ethylmaleimide, propylmaleimide, butylmaleimide, hexylmaleimide, octylmaleimide, dodecylmaleimide, stearylmaleimide, phenylmaleimide, cyclohexylmaleimide; and acrylonitriles such as acrylonitrile and methacrylonitrile Monomers; Amide group-containing vinyl monomers such as acrylamide and methacrylamide; Vinyl esters such as vinyl acetate, vinyl propionate, vinyl pivalate, vinyl benzoate and vinyl cinnamate; Alkenes such as ethylene and propylene; Butadiene and isoprene Conjugated dienes such as vinyl chloride, vinylidene chloride, allyl chloride, allyl alcohol and the like. These may be used alone or a plurality of these may be copolymerized.

  The main chain of the vinyl polymer (a2) is at least one monomer selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that the polymer is mainly produced by polymerization. Here, “mainly” means that 50 mol% or more, preferably 70% or more of the monomer units constituting the vinyl polymer are the above monomers.

  Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers, particularly preferred are acrylate monomers, and even more preferred is butyl acrylate. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid.

  Although not limited, it is preferable that the glass transition temperature of the vinyl polymer (a2) is lower than room temperature or use temperature for applications requiring rubber elasticity.

  The molecular weight distribution of the vinyl polymer (a2), that is, the ratio (Mw / Mn) of the weight average molecular weight and the number average molecular weight measured by GPC is not particularly limited, but is preferably less than 1.8, more preferably Is 1.7 or less, more preferably 1.6 or less, still more preferably 1.5 or less, particularly preferably 1.4 or less, and most preferably 1.3 or less. In the GPC measurement in the present invention, chloroform is usually used as the mobile phase, the measurement is performed with a polystyrene gel column, and the number average molecular weight and the like can be determined in terms of polystyrene.

  The number average molecular weight of the vinyl polymer (a2) is not particularly limited, but is preferably in the range of 500 to 1,000,000, more preferably 1,000 to 100,000, and 5,000 when measured by GPC. More preferred is ˜50,000.

  As the controlled radical polymerization for synthesizing the main chain of the vinyl polymer (a2), living radical polymerization is preferable, and among them, atom transfer radical polymerization is preferable.

  In atom transfer radical polymerization, an organic halide, particularly an organic halide having a highly reactive carbon-halogen bond (for example, a carbonyl compound having a halogen at the α-position or a compound having a halogen at the benzyl-position), or a sulfonyl halide. A compound or the like is used as an initiator. In order to obtain a polymer having two or more growth terminal structures in one molecule, it is preferable to use an organic halide having two or more starting points or a sulfonyl halide compound as an initiator. Specific examples of such an initiator include diethyl 2,5-dibromoadipate.

  There is no restriction | limiting in particular as a vinyl-type monomer used in this superposition | polymerization, All already illustrated can be used suitably.

Although it does not specifically limit as a transition metal complex used as a polymerization catalyst, Preferably it is a metal complex which uses a periodic table group 7, 8, 9, 10, or 11 element as a central metal. More preferred are complexes having a central metal of zero-valent copper, monovalent copper, divalent ruthenium, divalent iron or divalent nickel. Of these, a copper complex is preferable. Specific examples of monovalent copper compounds include cuprous chloride, cuprous bromide, cuprous iodide, cuprous cyanide, cuprous oxide, cuprous perchlorate, etc. is there. When a copper compound is used, 2,2′-bipyridyl and its derivatives, 1,10-phenanthroline and its derivatives, tetramethylethylenediamine, pentamethyldiethylenetriamine, hexamethyltris (2-aminoethyl) amine, etc. in order to increase the catalytic activity A ligand such as a polyamine is added. A preferred ligand is a nitrogen-containing compound, a more preferred ligand is a chelate-type nitrogen-containing compound, and a more preferred ligand is N, N, N ′, N ″, N ″ -pentamethyldiethylenetriamine. It is. A tristriphenylphosphine complex of divalent ruthenium chloride (RuCl ₂ (PPh ₃ ) ₃ ) is also suitable as a catalyst. When a ruthenium compound is used as a catalyst, an aluminum alkoxide is added as an activator. Furthermore, a divalent iron bistriphenylphosphine complex (FeCl ₂ (PPh ₃ ) ₂ ), a divalent nickel bistriphenylphosphine complex (NiCl ₂ (PPh ₃ ) ₂ ), and a divalent nickel bistributylphosphine A complex (NiBr ₂ (PBu ₃ ) ₂ ) is also suitable as a catalyst.

  The polymerization can be carried out without solvent or in various solvents. Solvent types include hydrocarbon solvents such as benzene and toluene, ether solvents such as diethyl ether and tetrahydrofuran, halogenated hydrocarbon solvents such as methylene chloride and chloroform, and ketones such as acetone, methyl ethyl ketone, and methyl isobutyl ketone. Solvents, alcohol solvents such as methanol, ethanol, propanol, isopropanol, n-butyl alcohol, t-butyl alcohol, nitrile solvents such as acetonitrile, propionitrile, benzonitrile, ester solvents such as ethyl acetate, butyl acetate, Examples thereof include carbonate solvents such as ethylene carbonate and propylene carbonate, and these can be used alone or in admixture of two or more.

  Moreover, although not limited, superposition | polymerization can be performed in 0 to 200 degreeC, Preferably it is 50 to 150 degreeC.

  The atom transfer radical polymerization of the present invention includes so-called reverse atom transfer radical polymerization. Reverse atom transfer radical polymerization is a high oxidation state when a normal atom transfer radical polymerization catalyst generates radicals, for example, peroxidation with respect to Cu (II ′) when Cu (I) is used as a catalyst. In this method, a general radical initiator such as a compound is allowed to act, and as a result, an equilibrium state similar to that of atom transfer radical polymerization is produced (see Macromolecules 1999, 32, 2872).

  The vinyl polymer (a2) has at least one crosslinkable silyl group. Further, from the viewpoint of the curability of the composition and the physical properties of the cured product, the number of crosslinkable silyl groups is preferably 1.1 or more and 4.0 or less, more preferably 1.2 or more and 3.5 or less on average. It is as follows.

  When a rubber property is particularly required for a cured product obtained by curing the curable composition of the present invention, the molecular weight between crosslinking points that greatly affects rubber elasticity can be increased. One is preferably at the end of the molecular chain. More preferably, it has all crosslinkable functional groups at the molecular chain ends.

  A method for producing a vinyl polymer having at least one crosslinkable silyl group at its molecular terminal, in particular, a (meth) acrylic polymer is disclosed in Japanese Patent Publication No. 3-14068, Japanese Patent Publication No. 4-55444, No. 6-211922 and the like. However, since these methods are free radical polymerization methods using the above "chain transfer agent method", the resulting polymer has a relatively high proportion of crosslinkable functional groups at the molecular chain ends, while Mw / Mn The value of the molecular weight distribution represented by is generally as large as 2 or more, and the viscosity is increased. Therefore, in order to obtain a vinyl polymer having a narrow molecular weight distribution and a low viscosity and having a crosslinkable functional group at the molecular chain terminal at a high ratio, the above “living radical polymerization method” is used. It is preferable.

  As the reactive silicon group of the vinyl polymer (a2), the reactive silicon group represented by the general formula (1) can be used in the same manner.

  Hereinafter, a method for introducing a silyl group into a vinyl polymer will be described, but the method is not limited thereto.

As a synthesis method of the vinyl polymer (a2) having at least one reactive silicon group,
(I) Method of adding a hydrosilane compound having a reactive silicon group to a vinyl polymer having at least one alkenyl group in the presence of a hydrosilylation catalyst (II) One molecule per vinyl polymer having at least one hydroxyl group A method of reacting a compound having a group capable of reacting with a reactive silicon group and a hydroxyl group such as an isocyanate group. (III) When a vinyl polymer is synthesized by radical polymerization, a polymerizable alkenyl group is contained in one molecule. (IV) Method of using a chain transfer agent having a reactive silicon group when synthesizing a vinyl polymer by radical polymerization (V) Highly reactive carbon-halogen Method of reacting a vinyl polymer having at least one bond with a compound having a reactive silicon group and a stable carbanion in one molecule And the like.

  Next, the vinyl polymer (a2) produced by the free radical polymerization method will be described.

  It does not specifically limit as a vinyl-type monomer, A various thing can be used and all the above-mentioned monomers can be used suitably.

  Although not limited, the main chain of the vinyl polymer (a2) is selected from the group consisting of (meth) acrylic monomers, acrylonitrile monomers, aromatic vinyl monomers, fluorine-containing vinyl monomers, and silicon-containing vinyl monomers. It is preferable that it is produced mainly by polymerizing at least one monomer. Here, “mainly” means that 50 mol% or more, preferably 70% or more of the monomer units constituting the vinyl polymer are the above monomers.

  Of these, a styrene monomer and a (meth) acrylic acid monomer are preferable from the physical properties of the product. More preferred are acrylate monomers and methacrylate monomers. In the present invention, these preferred monomers may be copolymerized with other monomers, and further block copolymerized, and in that case, these preferred monomers are preferably contained in a weight ratio of 40% or more. . In the above expression format, for example, (meth) acrylic acid represents acrylic acid and / or methacrylic acid. These may be used alone or a plurality of these may be copolymerized.

  The vinyl polymer (a2) may contain a monomer unit having copolymerizability with the above monomer unit such as a (meth) acrylic acid ester monomer. For example, carboxylic acid groups such as (meth) acrylic acid, amide groups such as (meth) acrylamide and N-methylol (meth) acrylamide, epoxy groups such as glycidyl (meth) acrylate, diethylaminoethyl (meth) acrylate, aminoethyl vinyl ether A monomer containing an amino group such as can be expected to have a copolymerization effect in terms of moisture curability and internal curability. Other examples include monomer units derived from acrylonitrile, styrene, α-methylstyrene, alkyl vinyl ether, vinyl chloride, vinyl acetate, vinyl propionate, ethylene, and the like.

  The number average molecular weight of the vinyl polymer (a2) in this case is not particularly limited, but when measured by GPC, those of 500 to 100,000 are preferred from the viewpoint of ease of handling. Furthermore, the thing of 5,000-30,000 is more preferable from the weather resistance of a hardened | cured material, and workability | operativity being favorable.

  A method for synthesizing the main chain of the vinyl polymer (a2) by free radical polymerization can be obtained by a usual vinyl polymerization method, for example, a solution polymerization method by radical reaction. The polymerization is usually carried out by adding the above-mentioned monomer, a radical initiator, a chain transfer agent and the like and reacting at 50 to 150 ° C.

  Examples of the radical initiator include 2,2′-azobisisobutyronitrile, 2,2′-azobis (2-methylbutyronitrile), 4,4′-azobis (4-cyanovaleric) acid. 1,1′-azobis (1-cyclohexanecarbonitrile), azobisisobutyric acid amidine hydrochloride, 2,2′-azobis (2,4-dimethylvaleronitrile) and other azo initiators, benzoyl peroxide, diperoxide Organic peroxide-based initiators such as -tert-butyl can be mentioned, but the use of azo-based initiators is preferred from the viewpoint of being not affected by the solvent used for polymerization and having a low risk of explosion and the like.

  Examples of chain transfer agents include n-dodecyl mercaptan, tert-dodecyl mercaptan, lauryl mercaptan, γ-mercaptopropyltrimethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyl Examples include mercaptans such as diethoxysilane and halogen-containing compounds.

  The polymerization may be performed in a solvent. Examples of the solvent are preferably non-reactive solvents such as ethers, hydrocarbons, and esters.

  In this case, the number of reactive silicon groups of the vinyl polymer (a2) is not particularly limited, but it is preferable to have one or more on average from the viewpoints of curability of the composition and physical properties of the cured product, More preferably 1.1 or more, still more preferably 1.2 or more, and still more preferably 1.5 or more.

  As the reactive silicon group of the vinyl polymer (a2), the reactive silicon group represented by the general formula (1) can be used in the same manner.

Examples of the method for introducing a reactive silicon group into the vinyl polymer (a2) of the present invention include a compound having both a polymerizable unsaturated bond and a reactive silicon group as a (meth) acrylic acid ester monomer. The method of copolymerizing with a unit is mentioned. The compound having both a polymerizable unsaturated bond and a reactive silicon group is represented by the general formula (6):
_{^{CH 2 = C (R 6)}} COOR 7 -Si (R 1 3-a) X a (6)
(Wherein R ⁶ represents a hydrogen atom or a methyl group, R ⁷ represents a divalent alkylene group having 1 to 6 carbon atoms. R ¹ , X, and a are the same as those in the general formula (1).)
Or general formula (7):
_{^{CH 2 = C (R 6)}} -Si (R 1 3-a) X a (7)
(In the formula, R ⁶ represents a hydrogen atom or a methyl group. R ¹ , X, and a are the same as those in the general formula (1).)
Monomers such as γ-methacryloxypropyl trimethoxysilane, γ-methacryloxypropylmethyldimethoxysilane, γ-methacryloxypropyl polyalkoxysilane such as γ-methacryloxypropyltriethoxysilane, and γ-acrylic. Γ-acryloxypropyl polyalkoxysilane such as loxypropyltrimethoxysilane, γ-acryloxypropylmethyldimethoxysilane, γ-acryloxypropyltriethoxysilane, vinyltrimethoxysilane, vinylmethyldimethoxysilane, vinyltriethoxysilane, etc. Examples thereof include vinyl alkyl polyalkoxysilane.

  In the case where the main chain skeleton of the component (A) is an oxyalkylene polymer, the curable composition of the present invention and the cured product containing the same have excellent low temperature characteristics, flexibility, and excellent compatibility with other components. Etc. can be given.

  Further, when the main chain skeleton of the component (A) is a vinyl polymer, in particular, a (meth) acrylic system, the weather resistance excellent in the curable composition of the present invention and the cured product containing the same by adjusting the monomer species, Flexibility, excellent compatibility with other components, and the like can be imparted.

  The main chain skeleton of the component (A) may be single, and by combining two or more kinds, it is possible to obtain a curable composition having the above characteristics and a cured product containing the same.

In the curable composition of the present invention, as the component (B), the following general formula (2):
—Si (R ² _3-b ) X _b (2)
(Wherein R ² represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an aralkyl group having 7 to 10 carbon atoms, X represents a hydroxyl group or a hydrolyzable group, and b represents 2) Or a silane coupling agent having a reactive silicon group and an amino group represented by (3) is preferably added. (B) It does not specifically limit as a component, A conventionally well-known thing can be used widely. Specific examples thereof include, for example, γ-aminopropyltrimethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltriisopropoxysilane, γ-aminopropylmethyldimethoxysilane, γ-aminopropylmethyldiethoxysilane, β-aminoethyltrimethoxysilane, β-aminoethyltriethoxysilane, β-aminoethylmethyldimethoxysilane, β-aminoethylmethyldiethoxysilane, α-aminomethyltrimethoxysilane, α-aminomethyltriethoxysilane, α -Aminomethyltriisopropoxysilane, α-aminomethylmethyldimethoxysilane, α-aminomethylmethyldiethoxysilane, α-aminomethyldiisopropoxysilane, 4-aminobutyltrimethoxysilane, 4-aminobutyltrie Xysilane, N-phenyl-γ-aminopropyltrimethoxysilane, N-phenyl-β-aminopropyltrimethoxysilane, N-phenyl-α-aminopropyltrimethoxysilane, N-phenyl-α-aminopropylmethyldimethoxysilane, N-phenyl-α-aminopropyltriethoxysilane, N-benzyl-γ-aminopropyltrimethoxysilane, N-benzyl-β-aminopropyltrimethoxysilane, N-benzyl-α-aminopropyltrimethoxysilane, N- Benzyl-α-aminopropylmethyldimethoxysilane, N-benzyl-α-aminopropyltriethoxysilane, N-vinylbenzyl-γ-aminopropyltrimethoxysilane, N-cyclohexyl-γ-aminopropyltrimethoxysilane, N-cyclohexyl -Γ-aminopropyltriethoxysilane, N-β- (aminoethyl) -γ-aminopropyltrimethoxysilane, N-β- (aminoethyl) -γ-aminopropyltriethoxysilane, N-β- (aminoethyl) ) -Γ-aminopropylmethyldimethoxysilane, N-β- (aminoethyl) -γ-aminopropylmethyldiethoxysilane, N- (6-aminohexyl) -γ-aminopropyltrimethoxysilane, N- (6 -Aminohexyl) -γ-aminopropyltriethoxysilane, N- (6-aminohexyl) -γ-aminopropylmethyldimethoxysilane, N- (6-aminohexyl) -γ-aminopropylmethyldiethoxysilane, and other amino acids Group-containing silanes; N- (1,3-dimethylbutylidene) -3- (triethoxysilyl) -1-pro Ketimines type silanes such as N'amin like.

  These components (B) may be used alone or in combination of two or more. By adding the component (B), adhesion to various adherends is improved. In particular, [gamma] -aminopropyltrimethoxysilane and N- [beta]-(aminoethyl)-[gamma] -aminopropyltrimethoxysilane are preferable from the viewpoints of ease of handling, availability, and adhesiveness.

  The amount of component (B) used is preferably from 0.1 to 20 parts by weight, more preferably from 0.5 to 10 parts by weight, based on 100 parts by weight of component (A). If it is less than 0.1 part by weight, the adhesiveness is lowered, and if it exceeds 20 parts by weight, the weather resistance is lowered.

  It is preferable to add asphalt as the component (C) to the curable composition of the present invention. (C) Asphalt of a component is not specifically limited, A conventionally well-known thing can be used widely. Specific examples thereof include natural asphalts such as Trinidad Epyle, Gilsonite, and burnt bitumen, as well as natural asphalt such as rock asphalt, cut back asphalt, straight asphalt and blown asphalt produced by petroleum refining processes, etc. Oil asphalt. In some cases, heavy oil catalytic cracking cycle oil, light oil catalytic cracking cycle oil, lubricating oil, and petroleum-based process oil that has been subjected to processing such as extraction, purification, hydrogenation, etc. of those fractions or other fractions. A mixture with such a substance may be used.

  These components (C) may be used alone or in combination of two or more. Addition of the component (C) improves the moisture permeability and water-resistant adhesion of the composition. In particular, straight asphalt is preferable from the viewpoints of compatibility with the component (A) and other components, dispersion stability, etc. Furthermore, straight asphalt having an asphaltene amount of 10% by weight or less facilitates dispersion stability and composition. This is preferable in that the viscosity can be reduced.

  The amount of asphaltene in the asphalt component can be measured based on a compositional analysis method by asphalt column chromatography (Japan Petroleum Institute Standard, JPI-5S-22-83).

  Further, coal tar produced by the coal refining process is classified as a bituminous substance like the asphalt described above, but it is not preferable because it contains harmful benzpyrene and has a large odor.

  As for the usage-amount of (C) component, 1-200 weight part is preferable with respect to 100 weight part of (A) component, More preferably, it is 5-100 weight part. If it is less than 1 part by weight, the moisture permeability and water-resistant adhesiveness are lowered, and if it exceeds 200 parts by weight, the viscosity is increased and workability is lowered, which is not preferable.

  It is preferable to add a plasticizer as the component (D) to the curable composition of the present invention. The plasticizer of component (D) is not particularly limited, and known ones can be used. Specific examples include phthalates such as dibutyl phthalate, diheptyl phthalate, di (2-ethylhexyl) phthalate, butyl benzyl phthalate, di-n-octyl phthalate, diisononyl phthalate, diisodecyl phthalate, diundecyl phthalate; Non-aromatic dibasic acid esters such as (2-ethylhexyl) adipate, di-n-octyl adipate, diisononyl adipate, diisodecyl adipate, di (2-ethylhexyl) sebacate, di2-ethylhexyl tetrahydrophthalate; paraffin base oil, Process oils such as naphthenic base oil and aroma base oil; fatty acid oils such as linseed oil, soybean oil, tung oil; alkyl esters made from fatty acids such as linseed oil, soybean oil, tung oil, castor oil, trimellitic acid tri-2 -D Aromatic esters such as ruhexyl and triisodecyl trimellitic acid; fatty acid esters such as male oleate, butyl oleate, methyl linoleate, methyl linolenate, methyl ricinoleate, methyl acetylricinoleate, pentaerythritol ester; polybutene, Polyvinyl oligomers such as hydrogenated polybutene and hydrogenated α-olefin oligomer; Hydrogenated polybutadiene oligomers such as hydrogenated liquid polybutadiene: Paraffin such as paraffin oil and chlorinated paraffin oil; Cycloparaffin such as naphthene oil; Biphenyl, triphenyl, etc. Aromatic oligomers of the following: complete or partial hydrogenation of aromatic oligomers; alkyl sulfonic acid ester compounds.

  These components (D) may be used alone or in combination of two or more. Addition of the component (D) reduces the viscosity of the composition and improves workability. Moreover, the compatibility and dispersion stability of the component (A) and the component (C) may be improved. In particular, phthalic acid esters, methyl esters using fatty acids such as soybean oil and castor oil as raw materials are preferable from the viewpoints of compatibility, dispersion stability, ease of handling, workability, and the like.

  Component (D) is preferably used in an amount of 10 to 120 parts by weight, more preferably 20 to 100 parts by weight, based on 100 parts by weight of component (A). If the amount is less than 10 parts by weight, the effect of decreasing the viscosity is small and the workability becomes insufficient. If the amount exceeds 120 parts by weight, sufficient mechanical properties such as a decrease in the tensile strength of the cured product cannot be obtained.

  It is preferable to add hydrophobic fine silica as the component (E) to the curable composition of the present invention. The hydrophobic fine powder silica of component (E) is not particularly limited, and conventionally known ones can be widely used. Specific examples thereof include those obtained by treating the surface of fumed silica (fumed silica) with various treatment agents. Fumed silica is silicon dioxide vaporized from silicon tetrachloride and hydrolyzed in a hot flame. Aggregated particles or agglomerated particles are formed which are composed of spherical primary particles without pores, but are strongly agglomerated in the production process. Siloxane and silanol groups are present on the surface of these particles, and hydrophobicity is imparted by chemically reacting silanes or silazanes with the silanol groups. Specific examples of the surface treatment agent include dimethyldichlorosilane, silicone oil, hexamethyldisilazane, octylsilane, hexadecylsilane, aminosilane, methacrylsilane, octamethylcyclotetrasiloxane, and polydimethylsiloxane. . Hydrophobizing the surface reduces water adsorption and facilitates dispersion in an organic polymer having a reactive silicon group as component (A).

  Specific product names include Aerosil DT4, Aerosil NA200Y, Aerosil NA50H, Aerosil NA50Y, Aerosil NAX50, Aerosil R104, Aerosil R106, Aerosil R202, Aerosil R202W90, Aerosil R504, Aerosil R711, Aerosil R700, Aerosil R7200, Aerosil R805VV90, Aerosil R812, Aerosil R812S, Aerosil R816, Aerosil R8200, Aerosil R972, Aerosil R972V, Aerosil R974, Aerosil RA200HS, Aerosil RX200, Aerosil RX300Y, Aerosil RX200Y, Aerosil RR200Y Degussa's products such as 0 can be exemplified.

  These (E) components may be used independently and may be used together 2 or more types. By adding the component (E), the dispersion stability of the composition is improved, and the storage stability is improved accordingly. In particular, when the viscosity of the composition is lowered in order to improve workability, the dispersion stability of the component (A) and the component (C) is lowered and tends to be easily separated after storage. However, by combining the constituent components of the present invention including the present component (E), the dispersion stability is greatly improved, and sufficient storage stability can be obtained. The separation after storage refers to a phenomenon in which a liquid component composed of a low viscosity component is separated during storage of the composition in a closed container. Also, when non-surface-treated fumed silica, natural silica, or humidity synthetic silica is used as the component (E), it is not preferable because sufficient dispersion stability cannot be obtained.

The particle size of the hydrophobic fine powder silica is not particularly limited, specific surface area (according to BET adsorption method) is preferably ^{10 m} 2 / g or more, more preferably 30~500m ² / g, more preferably 50 to 300 m ² Silica in the form of ultrafine powder of about / g is preferable. The BET adsorption method is a method in which an inert gas molecule whose adsorption occupation area is known is physically adsorbed on the surface of powder particles at the temperature of liquid nitrogen, and the specific surface area of the sample is obtained from the amount.

  (E) As for the usage-amount of a component, 1-20 weight part is preferable with respect to 100 weight part of (A) component, More preferably, it is 2-10 weight part. If it is less than 1 part by weight, the effect of stabilizing the dispersion is insufficient, and if it exceeds 20 parts by weight, the viscosity of the system increases and the workability decreases, which is not preferable.

It is preferable to add an inorganic filler as the component (F) to the curable composition of the present invention. The inorganic filler of component (F) is not particularly limited, and conventionally known inorganic fillers can be widely used. Specific examples thereof include, for example, heavy calcium carbonate, colloidal calcium carbonate, magnesium carbonate, titanium oxide, cinnabar, crushed stone, gravel, carbon black, kaolin, clay, talc, silicic anhydride, quartz powder, aluminum powder, zinc powder. Glass fiber, carbon fiber, synthetic fiber, alumina, shirasu balloon, fly ash, fly ash balloon, cement, calcium oxide and the like. These components (F) may be used alone or in combination of two or more. By using the component (F), the dispersion stability and sagging property of the composition are improved. In particular, calcium carbonate and fly ash are preferable from the viewpoints of ease of handling, availability, and cost.
(F) As for the usage-amount of a component, 10-500 weight part is preferable with respect to 100 weight part of (A) component, More preferably, it is 50-400 weight part. If it is less than 10 parts by weight, it is insufficient from the viewpoint of dispersion stability and cost, and if it exceeds 500 parts by weight, it is not preferable because the viscosity of the system is increased and workability is lowered.

  It is preferable to add a curing catalyst as the component (G) to the curable composition of the present invention. The curing catalyst for the component (G) is not particularly limited, and conventionally known ones can be widely used. Specific examples thereof include, for example, titanium compounds such as tetrabutyl titanate, tetraisopropyl titanate, titanium tetraacetylacetonate; dibutyltin dilaurate, bis (dibutyltin laurate) oxide, dibutyltin malate, dibutyltin phthalate, dibutyltin dioctate, dibutyltin Diethylhexanoate, dibutyltin dimethylmalate, dibutyltin diethylmalate, dibutyltin dibutylmalate, dibutyltin dioctylmalate, dibutyltin ditridecylmalate, dibutyltin dibenzylmalate, dibutyltin diacetate, dioctyltin diethylmalate, dioctyltin dioctyl Malate, dibutyltin dimethoxide, dibutyltin dinonylphenoxide, dibutenyltin Xylose, dibutyltin bisacetylacetonate, dibutyltin bisethylacetoacetonate, reaction product of dibutyltin oxide and phthalate, reaction product of dibutyltin oxide and maleate, reaction product of dibutyltin oxide and ethyl silicate, dibutyltin dialchelate Tetravalent tin compounds such as a reaction product of ethyl silicate with divalent tin compounds such as tin octylate, tin naphthenate, tin stearate and versatic acid; aluminum trisacetylacetonate, aluminum trisethylacetoacetate, di Organoaluminum compounds such as isopropoxyaluminum ethyl acetoacetate; Zirconium compounds such as zirconium tetraacetylacetonate; Bismuth tris Sanoate); zinc octylate; butylamine, octylamine, dibutylamine, monoethanolamine, diethanolamine, triethanolamine, diethylenetriamine, triethylenetetramine, laurylamine, oleylamine, cyclohexylamine, benzylamine, diethylaminopropylamine, xylylenediamine, Triethylenediamine, guanidine, phenylguanidine, diphenylguanidine, tolylbiguanide, 2,4,6-tris (dimethylaminomethyl) phenol, morpholine, N-methylmorpholine, 2-ethyl-4-methylimidazole, 1,8-diazabicyclo ( 5,4,0) amine compounds such as undecene-7 (DBU), or salts of these amine compounds with carboxylic acids, etc .; Examples include low molecular weight polyamide resins obtained from amines and polybasic acids; reaction products of excess polyamines and epoxy compounds, and other known silanol condensation catalysts such as other acidic catalysts and basic catalysts.

  These (G) components may be used independently and may be used together 2 or more types. Addition of the component (G) can impart appropriate curability to the composition. In particular, tetravalent tin compounds, combinations of divalent tin compounds and amines, and amine compounds such as phenylguanidine and tolylbiguanide are preferred from the viewpoints of ease of handling, curability, mechanical properties, adhesiveness, etc. The tin compound is more preferable from the viewpoints of adhesiveness and cost.

  As for the usage-amount of (G) component, 0.1-10 weight part is preferable with respect to 100 weight part of (A) component, More preferably, it is 0.2-8 weight part. If the amount is less than 0.1 parts by weight, sufficient curability cannot be obtained. If the amount exceeds 10 parts by weight, bleeding to the adhesive interface occurs and the adhesiveness is lowered.

In the curable composition of the present invention, in order to further enhance the activity of the component (G), the general formula R ¹⁴ _-a Si (OR ¹ ) _a (wherein R ¹ and a are the general formula (1)). It is also possible to add a silicon compound represented by The silicon compound is not limited, but is directly connected to the Si atom in the general formula such as phenyltrimethoxysilane, phenylmethyldimethoxysilane, phenyldimethylmethoxysilane, diphenyldimethoxysilane, diphenyldiethoxysilane, triphenylmethoxysilane and the like. It is preferable that at least one R ¹ is an aryl group having 6 to 20 carbon atoms because the effect of accelerating the curing reaction of the composition is great. In particular, diphenyldimethoxysilane and diphenyldiethoxysilane are particularly preferable because of low cost and easy availability. The compounding amount of the silicon compound is preferably about 0.01 to 10 parts by weight, more preferably 0.1 to 8 parts by weight, based on 100 parts by weight of the total amount of the organic polymer (A) having a reactive silicon group. When the compounding amount of the silicon compound is below this range, the effect of accelerating the curing reaction may be reduced. On the other hand, when the compounding amount of the silicon compound exceeds this range, the hardness and tensile strength of the cured product may decrease.

  It is preferable to add a tackifier resin as the component (H) to the curable composition of the present invention. The tackifying resin of component (H) is not particularly limited, and conventionally known ones can be widely used. Specific examples thereof include, for example, terpene resins, aromatic modified terpene resins and hydrogenated terpene resins obtained by hydrogenation thereof, terpene phenol resins obtained by modifying terpene resins with phenols, phenol resins, modified phenol resins, xylene resins, xylenes. Phenol resin, cyclopentadiene phenol resin, coumarone indene resin, rosin resin, rosin ester resin, hydrogenated rosin ester resin, low molecular weight polystyrene resin, petroleum resin (aliphatic hydrocarbon resin, aromatic hydrocarbon resin, aliphatic / Aromatic mixed hydrocarbon resins, heat-reactive hydrocarbon resins, etc.), hydrogenated petroleum resins, phenol-modified petroleum resins obtained by modifying petroleum resins with phenols, and these hydrogenated resins and DCPD resins.

  These (H) components may be used independently and may be used together 2 or more types. By adding the component (H), the compatibility and dispersion stability of the component (A) and the component (C) are improved. In particular, a terpene phenol resin, an aromatic hydrocarbon resin, a mixed aliphatic / aromatic hydrocarbon resin, or a resin obtained by modifying these with (alkyl) phenol is preferable from the viewpoint of easy handling and dispersion stability.

  The amount of component (H) used is preferably 1 to 80 parts by weight, more preferably 2 to 70 parts by weight per 100 parts by weight of component (A). If the amount is less than 1 part by weight, the dispersion stability tends to decrease. If the amount exceeds 80 parts by weight, the viscosity increases, and the workability decreases.

  A silane coupling agent, a thixotropic agent, an epoxy resin, a stabilizer, and the like can be added to the curable composition of the present invention as necessary.

  Specific examples of the silane coupling agent include γ-isocyanatopropyltrimethoxysilane, γ-isocyanatopropyltriethoxysilane, γ-isocyanatopropylmethyldiethoxysilane, γ-isocyanatopropylmethyldimethoxysilane, and (isocyanatemethyl) trimethoxysilane. , (Isocyanatemethyl) dimethoxymethylsilane and other isocyanate group-containing silanes; γ-mercaptopropyltrimethoxysilane, γ-mercaptopropyltriethoxysilane, γ-mercaptopropylmethyldimethoxysilane, γ-mercaptopropylmethyldiethoxysilane, mercapto Mercapto group-containing silanes such as methyltriethoxysilane; γ-glycidoxypropyltrimethoxysilane, γ-glycidoxypropyltriethoxy Epoxy group-containing silanes such as silane, γ-glycidoxypropylmethyldimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltrimethoxysilane, β- (3,4-epoxycyclohexyl) ethyltriethoxysilane; Carboxysilanes such as carboxyethyltriethoxysilane, β-carboxyethylphenylbis (2-methoxyethoxy) silane, N-β- (carboxymethyl) aminoethyl-γ-aminopropyltrimethoxysilane; vinyltrimethoxysilane; Vinyltriethoxysilane, γ-methacryloyloxypropyltrimethoxysilane, γ-methacryloyloxypropyltriethoxysilane, γ-acryloyloxypropyltrimethoxysilane, γ-acryloyloxypropyltriethoxysilane, etc. Halogen-containing silanes of γ- chloropropyl trimethoxysilane; vinyl-type unsaturated group-containing silanes tris isocyanurate silanes such as (trimethoxysilyl) isocyanurate and the like. Moreover, the condensate which condensed the said silane partially can also be used. Furthermore, amino-modified silyl polymers, silylated amino polymers, unsaturated aminosilane complexes, phenylamino long-chain alkylsilanes, aminosilylated silicones, silylated polyesters and the like, which are derivatives of these, can also be used as silane coupling agents. . Silicates such as methyl silicate and ethyl silicate can also be used. These may be used alone or in combination of two or more. Addition of the silane coupling agent improves the storage stability and adhesiveness of the composition. In particular, vinyl trimethoxysilane and its condensates, vinyl-type unsaturated group-containing silanes such as γ-methacryloyloxypropyltrimethoxysilane, and silicates such as methyl silicate are available, easy to handle, and storage stable. It is preferable from the point of the effect. 0.1-20 weight part is preferable with respect to 100 weight part of (A) component, and, as for the usage-amount of a silane coupling agent, More preferably, it is 0.5-10 weight part. If the amount is less than 0.1 parts by weight, the storage stability tends to decrease. If the amount exceeds 20 parts by weight, it is not preferable because it bleeds to the adhesive interface and the adhesiveness decreases.

  Specific examples of the thixotropic agent include hydrogenated castor oil, organic amide wax, organic bentonite, and calcium stearate. These may be used alone or in combination of two or more. The thixotropic agent is preferably 0.1 to 20 parts by weight, more preferably 0.5 to 10 parts by weight, based on 100 parts by weight of component (A). If the amount is less than 0.1 parts by weight, sufficient thixotropy may not be obtained. If the amount exceeds 20 parts by weight, the viscosity increases and the workability decreases.

  Specific examples of the epoxy resin include, for example, epichlorohydrin-bisphenol A type epoxy resin, epichlorohydrin-bisphenol F type epoxy resin, flame retardant type epoxy resin such as glycidyl ether of tetrabromobisphenol A, novolac type epoxy resin, hydrogenated bisphenol A, and the like. Type epoxy resin, glycidyl ether type epoxy resin of bisphenol A propylene oxide adduct, p-oxybenzoic acid glycidyl ether ester type epoxy resin, m-aminophenol type epoxy resin, diaminodiphenylmethane type epoxy resin, urethane-modified epoxy resin, various fats Cyclic epoxy resin, N, N-diglycidylaniline, N, N-diglycidyl-o-toluidine, triglycidyl isocyanurate, polyalkylene glycol jig Examples include glycidyl ethers of polyhydric alcohols such as sidyl ether and glycerin, epoxidized products of unsaturated polymers such as hydantoin-type epoxy resins and petroleum resins, but are not limited to these and are generally used. Epoxy resins can be used. These may be used alone or in combination of two or more. Addition of the epoxy resin may improve the mechanical properties and water-resistant adhesion of the cured product, and may improve the compatibility and dispersion stability of the component (A) and the component (C). In particular, bisphenol A type epoxy resins are preferable from the balance of availability, ease of handling, mechanical properties, water-resistant adhesion, and the like. As for the usage-amount of an epoxy resin, 1-200 weight part is preferable with respect to 100 weight part of (A) component, More preferably, it is 5-100 weight part. If it is less than 1 part by weight, sufficient mechanical properties and water-resistant adhesion cannot be obtained, and if it exceeds 200 parts by weight, the cured product becomes too hard.

  There is no limitation in particular as a hardening | curing agent for epoxy resins, The well-known hardening | curing agent for epoxy resins can be used. Specifically, for example, triethylenetetramine, tetraethylenepentamine, diethylaminopropylamine, N-aminoethylpiperidine, m-xylylenediamine, m-phenylenediamine, diaminodiphenylmethane, diaminodiphenylsulfone, isophoronediamine, amine-terminated poly Primary and secondary amines such as ether; tertiary amines such as 2,4,6-tris (dimethylaminomethyl) phenol and tripropylamine, and salts of these tertiary amines; polyamide resins; imidazoles; Dicyandiamides; Ketimine compounds that are dehydration condensates of various amine compounds and ketone compounds; Boron trifluoride complex compounds, phthalic anhydride, hexahydrophthalic anhydride, tetrahydrophthalic anhydride, dodecynyl succinic anhydride, pyromellitic anhydride , Alcohols; carboxylic anhydrides such as water Kuroren acid phenol; carboxylic acids; but aluminum or compounds of diketone complex compounds such as zirconium can be exemplified, but the invention is not limited thereto. The curing agents may be used alone or in combination of two or more. The amount of the curing agent used is preferably in the range of 0.1 to 100 parts by weight with respect to 100 parts by weight of the epoxy resin.

  Specific examples of the stabilizer include an antioxidant, a light stabilizer, and an ultraviolet absorber.

  When antioxidant is used, the heat resistance of hardened | cured material can be improved. Examples of the antioxidant include hindered phenols, amines, and polyphenols, with hindered phenols being particularly preferred. The amount of the antioxidant used is preferably 0.1 to 10 parts by weight, more preferably 0.2 to 5 parts by weight, based on 100 parts by weight of component (A).

  When a light stabilizer is used, photooxidation deterioration of the cured product can be prevented. Examples of the light stabilizer include benzotriazole-based, hindered amine-based, and benzoate-based compounds, and hindered amine-based compounds are particularly preferable. It is preferable to use 0.1-10 weight part with respect to 100 weight part of (A) component, and, as for the usage-amount of a light stabilizer, it is still more preferable to use 0.2-5 weight part.

  When the ultraviolet absorber is used, the surface weather resistance of the cured product can be enhanced. Examples of ultraviolet absorbers include benzophenone-based, benzotriazole-based, salicylate-based, substituted tolyl-based, and metal chelate-based compounds, and benzotriazole-based compounds are particularly preferable. It is preferable to use 0.1-10 weight part with respect to 100 weight part of (A) component, and, as for the usage-amount of a ultraviolet absorber, it is still more preferable to use 0.2-5 weight part.

  Furthermore, you may add various additives to the curable composition of this invention as needed for the purpose of adjustment of various physical properties of a curable composition or hardened | cured material. Examples of such additives include, for example, flame retardants, curability modifiers, radical inhibitors, metal deactivators, antiozonants, lubricants, pigments, foaming agents, solvents, fungicides and the like. It is done. These various additives may be used alone or in combination of two or more.

  The curable composition of the present invention can also be prepared as a one-component type in which all the blended components are pre-blended and sealed and cured by moisture in the air after construction. It is also possible to prepare a two-component type in which components such as a plasticizer and water are blended and the compounding material and the polymer composition are mixed before use.

  The viscosity of the curable composition of the present invention is that the viscosity (2 rpm, rotor No. 7, BS type viscometer) measured in accordance with JIS K-7117 is 800 Pa · s or less at 23 ° C., It is preferable from the viewpoints of the dischargeability and flowability of the composition (in the case of the two-component type, the composition after mixing the main agent and the curing agent), stretching workability by combing irons, etc., and more preferably 500 Pa · s or less. It is preferable from the viewpoint of workability in winter. In addition, when the viscosity of the composition obtained by mixing an organic polymer containing a reactive silicon group and asphalt is set to 800 Pa · s or less in the composition outside the present invention, the dispersion stability of both components cannot be obtained and is practical. It is not preferable because stable storage stability cannot be obtained.

  The method for preparing the curable composition of the present invention is not particularly limited. For example, the above-described components are blended and kneaded using a mixer, roll, kneader or the like at room temperature or under heating, or a small amount of a suitable solvent is used. Ordinary methods such as dissolving and mixing the components can be used.

  Although it does not specifically limit as a use for which the curable composition of this invention is used, It can utilize effectively as a waterproofing material, sealing material, an adhesive agent, etc. for construction and civil engineering. In particular, since this composition has no odor and is excellent in workability, general-purpose adhesiveness, moisture permeability resistance, and water-resistant adhesiveness, solvent-based asphalt and water-based asphalt used as waterproofing materials, sealing materials, and adhesives in the waterproof field. It is useful as an alternative to

In order to further clarify the present invention, specific examples will be described below, but the present invention is not limited thereto.
(Synthesis Example 1)
Polymerization of propylene oxide with a zinc hexacyanocobaltate glyme complex catalyst using a 1/1 (weight ratio) mixture of polyoxypropylene diol having a number average molecular weight of 2,000 and polyoxypropylene triol having a number average molecular weight of 3,000 as an initiator. As a result, a polyoxypropylene diol having a number average molecular weight of 19,800 (polystyrene converted molecular weight determined from GPC) was obtained. After the sodium methoxide was reacted with the obtained polymer, allyl chloride was reacted to convert the terminal hydroxyl group into an unsaturated group. Subsequently, 0.72 [eq / unsaturated group] mole of dimethoxymethylsilane was reacted in the presence of chloroplatinic acid, and the number average molecular weight of 20 having 70% ( ¹ H-NMR analysis) of dimethoxymethylsilyl group at the molecular end. 000 polyoxypropylene polymer was obtained (Polymer A).
(Synthesis Example 2)
After 800 g of polyoxypropylene diol having a number average molecular weight of 5,200 and 50.2 g of isophorone diisocyanate were mixed in a pressure-resistant reaction vessel equipped with a stirrer, 0.8 g of tin catalyst (10% DOP solution of dibutyltin dilaurate) was added. By stirring at 80 ° C. for 4 hours, an isocyanate group-terminated polymer having a molecular weight of about 15,000 was obtained (molecular weight calculated from titration value (0.579%) of isocyanate group). After cooling to 60 ° C., γ-aminopropyltrimethoxysilane 1.0 [eq / NCO group] is added and stirred for about 30 minutes, whereby the number average molecular weight having a trimethoxysilyl group at the molecular end is 17,000 ( A polyoxypropylene polymer having a molecular weight of polystyrene determined by GPC was obtained (Polymer B).
(Synthesis Example 3)
A polyoxypropylene diol having a number average molecular weight of 2,000 is used as an initiator, and propylene oxide is polymerized using a zinc hexacyanocobaltate glyme complex catalyst to obtain a number average molecular weight of 22,500 (polystyrene equivalent molecular weight determined by GPC). A polyoxypropylene diol was obtained. By adding γ-isocyanatopropyltrimethoxysilane 0.8 [eq / unsaturated group] to the obtained polymer and reacting at 90 ° C. for 5 hours, the number average molecular weight having a trimethoxysilyl group at the molecular terminal is 24. 1,000 polyoxypropylene polymers were obtained (Polymer C).
(Synthesis Example 4)
In 43 g of toluene heated to 110 ° C., 6.0 g of butyl acrylate, 66 g of methyl methacrylate, 13 g of stearyl methacrylate, 5.4 g of γ-methacryloxypropylmethyldimethoxysilane, 7.0 g of γ-mercaptopropylmethyldimethoxysilane and toluene A solution prepared by dissolving 2.6 g of azobisisobutyronitrile as a polymerization initiator in a 23 g mixture was dropped over 4 hours, followed by 2 hours of polymerization, and a solid content concentration of 60%, which was measured by GPC (polystyrene conversion). A copolymer having an average molecular weight of 2,200 was obtained.

The obtained polymer and the polymer A obtained in Synthesis Example 1 were blended at a solid content ratio (weight ratio) of 40/60, and the volatile content was devolatilized (110 ° C., reduced pressure) with an evaporator to obtain a solid content concentration. 99% or more of a transparent and viscous liquid was obtained (Polymer D).
(Synthesis Example 5)
8.39 g (58.5 mmol) of cuprous bromide and 112 mL of acetonitrile were charged, and the mixture was heated and stirred at 70 ° C. for 30 minutes under a nitrogen stream. To this were added 17.6 g (48.8 mmol) of diethyl 2,5-dibromoadipate and 224 mL (1.56 mol) of butyl acrylate, and the mixture was heated and stirred at 70 ° C. for 45 minutes. To this, 0.41 mL (1.95 mmol) of pentamethyldiethylenetriamine (hereinafter referred to as triamine) was added to initiate the reaction. Subsequently, heating and stirring were continued at 70 ° C., and 895 mL (6.24 mol) of butyl acrylate was intermittently added dropwise over 160 minutes from 80 minutes after the start of the reaction. During this period, 1.84 mL (8.81 mmol) of triamine was added. 375 minutes after the start of the reaction, 288 mL (1.95 mol) of 1,7-octadiene and 4.1 mL (19.5 mmol) of triamine were added, and the mixture was continuously heated and stirred at 70 ° C., and the heating was stopped 615 minutes after the start of the reaction. did. The reaction solution was diluted with toluene and filtered, and the filtrate was heated under reduced pressure to obtain a polymer [1]. The number average molecular weight of the obtained polymer [1] is 24,000, the molecular weight distribution is 1.3, and the number of alkenyl groups per polymer molecule determined by ¹ H-NMR analysis is 2.6. there were.

  Under a nitrogen atmosphere, a 2 L flask was charged with the polymer [1], potassium acetate 11.9 g (0.121 mol), N, N-dimethylacetamide (hereinafter also referred to as DMAc) 900 mL, and heated and stirred at 100 ° C. for 11 hours. did. The reaction solution was heated under reduced pressure to remove DMAc, added with toluene and filtered. An adsorbent (200 g, manufactured by Kyowa Chemical Co., Ltd., Kyoward 700PEL) was added to the filtrate, and the mixture was heated and stirred at 100 ° C. for 3 hours under a nitrogen stream. After removing the adsorbent by filtration, the toluene in the filtrate was distilled off under reduced pressure to obtain a polymer [2].

In a 1 L pressure-resistant reactor, polymer [2] (648 g), dimethoxymethylhydrosilane (25.5 mL, 0.207 mol), methyl orthoformate (7.54 mL, 0.0689 mol), and 1,1, 3,3-tetramethyl-1,3-divinyldisiloxane complex was charged. However, the amount of the platinum catalyst used was 3 × 10 ⁻³ equivalent in terms of molar ratio to the alkenyl group of the polymer. The mixture was heated and stirred at 100 ° C. for 2 hours. The volatile component of the mixture was distilled off under reduced pressure to obtain a silyl group-terminated polymer (Polymer E). The number average molecular weight of the obtained polymer was 30,000 by GPC measurement (polystyrene conversion), and the molecular weight distribution was 1.8. When the average number of silyl groups introduced per molecule of the polymer was determined by ¹ H-NMR analysis, it was 1.9.
(Examples 1-20, Comparative Examples 1-20)
Using the polymers obtained in Synthesis Examples 1 to 5, a one-component curable composition having the composition shown in Table 1 was prepared, and the following evaluation was performed.
(1) Workability: A BS viscometer was used to measure the viscosity of the curable composition at a rotation speed of 2 rpm (No. 7 rotor, temperature 23 ° C.). In the determination, a case where the viscosity value is less than 500 Pa · s is indicated as “◯”, a case where the viscosity value is 500 Pa · s or more and less than 800 Pa · s is indicated as “Δ”, and a case where the viscosity value is 800 Pa · s or more is indicated as “X”.
(2) Curability: The curable composition was discharged onto a metal can, the surface of the composition was touched with a spatula over time, and the time until the composition did not adhere to the spatula was measured. Evaluation is 23 ° C., 50% R.D. H. The test was carried out under the conditions of (relative humidity). In the judgment, the case of less than 2 hours was evaluated as ◯, the case of from 2 hours to less than 24 hours was evaluated as Δ, and the case of 24 hours or more was evaluated as ×.
(3) Adhesiveness: The curable composition was applied in the form of a bead (width: about 10 mm, thickness: 4 to 8 mm) to the back surface of the asphalt waterproof sheet with sand, and 23 ° C., 50% R.D. H. It was cured for 1 week under the condition of (relative humidity). After curing, an incision of about 10 mm was made at the bonding interface with a razor blade, and the fractured state was observed when pulled in the direction of about 180 degrees. In the judgment, the case of cohesive failure was indicated by ◯, the case of cohesive failure and interfacial failure being mixed, and the case of interfacial failure being ×.
(4) Storage stability: After producing a curable composition, it was stored in a sealed state (23 ° C.), and the composition was taken out over time and observed for separation (visual observation). In the judgment, the case where it was not separated for 12 weeks or more was marked as ◯, the case where it was separated between 4 weeks and 12 weeks, and the case where it was separated within 4 weeks as x.

  The evaluation results are shown in Tables 1 and 2.

以上、実施例に記載の硬化性組成物は、作業性や硬化性が良好でかつ接着性や貯蔵安定性が良好であった。一方、比較例の組成物では、これら物性をバランス良く発現する系は見られなかった。

As mentioned above, the curable composition as described in an Example had favorable workability | operativity and sclerosis | hardenability, and favorable adhesiveness and storage stability. On the other hand, in the composition of the comparative example, a system that expresses these physical properties in a balanced manner was not found.

Claims (12)

(A) The following general formula (1):
-Si (R ¹ _3-a ) X _a (1)
(In the formula, R ¹ represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, X represents a hydroxyl group or a hydrolyzable group. 2 or 3 is shown.)
100 parts by weight of an organic polymer having a reactive silicon group represented by
(B) In one molecule, the following general formula (2):
-Si (R ² _3-b ) X ² _b (2)
(In the formula, R ² represents an alkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, and an aralkyl group having 7 to 10 carbon atoms, and X ² represents a hydroxyl group or a hydrolyzable group. 2 or 3)) 0.1-20 parts by weight of a silane coupling agent having a reactive silicon group and an amino group represented by
(C) 1 to 200 parts by weight of asphalt,
(D) 10 to 120 parts by weight of a plasticizer,
(E) 1 to 20 parts by weight of hydrophobic finely divided silica,
(F) 10 to 500 parts by weight of an inorganic filler,
(G) 0.1 to 10 parts by weight of a curing catalyst ,
(H) The viscosity (2 rpm, rotor No. 7, BS type viscometer) which contains 1 to 80 parts by weight of a tackifying resin and is measured by a method according to JIS K 7117 is 800 Pa at 23 ° C. -The curable composition characterized by being below s. (A) component, according to claim 1, characterized in that the polyoxyalkylene polymer having a reactive silicon group represented by the general formula (1) (a1) and / or the vinyl polymer (a2) the curable composition according to. The curable composition according to claim 2 , wherein the main chain skeleton of the component (a1) is a polyoxypropylene polymer. The curable composition according to claim 2 or 3 , wherein the main chain skeleton of the component (a2) is a (meth) acrylic acid alkyl ester copolymer. The curable composition according to any one of claims 1 to 4 , wherein the asphaltene contained in the asphalt (C) is 10% by weight or less. Component (E) The curable composition according to any one of claims 1 to 5, characterized in that a surface treated fumed silica. The (H) component is a terpene phenol resin, aromatic hydrocarbon resin , aliphatic / aromatic mixed hydrocarbon resin, or aromatic hydrocarbon resin or mixed aliphatic / aromatic hydrocarbon resin with (alkyl) phenol. The curable composition according to any one of claims 1 to 6 , wherein the curable composition is at least one of modified resins. Component (D) The curable composition according to any one of claims 1 to 7, characterized in that an ester compound. Viscosity measured by a method conforming to JIS K 7117 (2 rpm, rotor No.7, BS type viscometer) is in any one of claims 1-8, characterized in that at most 500 Pa · s at 23 ° C. The curable composition as described. Waterproof material formed using the curable composition according to any one of claims 1-9. Adhesive comprising the curable composition according to any one of claims 1-9. Sealing material formed using the curable composition according to any one of claims 1-9.